Controlling the thermal switching in upconverting nanoparticles through surface chemistry.

Photon upconversion taking place in small rare-earth-doped nanoparticles has been recently observed to be thermally modulated in an anomalous manner, showing thermal enhancement of the emission intensity. This effect was proved to be linked to the role of adsorbed water molecules as surface quenchers. The surface capping of the particles has a direct influence on the thermal dynamics of water adsorption and desorption, and therefore on the optical properties. Here, we show that the upconversion intensity of small-size (<25 nm) nanoparticles co-doped with Yb3+ and Er3+ ions, and functionalized with different capping molecules, presents clear irreversibility patterns upon thermal cycling that strongly depend on the chemical nature of the nanoparticle surface. By performing temperature-controlled luminescence measurements we observed the formation of a thermal hysteresis loop, resembling an optical switching phenomenon, whose shape and trajectory depend on the hydrophilicity of the surface. Additionally, an intensity overshoot takes place immediately after turning off the heating source, affecting each radiative transition differently. We performed numerical modelling to understand this effect considering non-radiative energy transfer from the surface defect states to the Er3+ ions. These findings are relevant for the comprehension of nanoparticle-based luminescence and the interplay between the surface and volume effects, and more generally, for applications involving UCNPs such as nanothermometry and bioimaging, and the development of optical encoding systems.

Self-Calibrated Double Luminescent Thermometers Through Upconverting Nanoparticles.

Luminescent nanothermometry uses the light emission from nanostructures for temperature measuring. Non-contact temperature readout opens new possibilities of tracking thermal flows at the sub-micrometer spatial scale, that are altering our understanding of heat-transfer phenomena occurring at living cells, micro electromagnetic machines or integrated electronic circuits, bringing also challenges of calibrating the luminescent nanoparticles for covering diverse temperature ranges. In this work, we report self-calibrated double luminescent thermometers, embedding in a poly(methyl methacrylate) film Er3+- and Tm3+-doped upconverting nanoparticles. The Er3+-based primary thermometer uses the ratio between the integrated intensities of the 2 H 11 / 2 → 4 I15/2 and 4 S 3 / 2 → 4 I15/2 transitions (that follows the Boltzmann equation) to determine the temperature. It is used to calibrate the Tm3+/Er3+ secondary thermometer, which is based on the ratio between the integrated intensities of the 1 G 4 → 3 H6 (Tm3+) and the 4 S 3 / 2 → 4 I15/2 (Er3+) transitions, displaying a maximum relative sensitivity of 2.96% K-1 and a minimum temperature uncertainty of 0.07 K. As the Tm3+/Er3+ ratio is calibrated trough the primary thermometer it avoids recurrent calibration procedures whenever the system operates in new experimental conditions.

Upconversion Nanocomposite Materials With Designed Thermal Response for Optoelectronic Devices.

Upconversion is a non-linear optical phenomenon by which low energy photons stimulate the emission of higher energy ones. Applications of upconversion materials are wide and cover diverse areas such as bio-imaging, solar cells, optical thermometry, displays, and anti-counterfeiting technologies, among others. When these materials are synthesized in the form of nanoparticles, the effect of temperature on the optical emissions depends critically on their size, creating new opportunities for innovation. However, it remains a challenge to achieve upconversion materials that can be easily processed for their direct application or for the manufacture of optoelectronic devices. In this work, we developed nanocomposite materials based on upconversion nanoparticles (UCNPs) dispersed in a polymer matrix of either polylactic acid or poly(methyl methacrylate). These materials can be processed from solution to form thin film multilayers, which can be patterned by applying soft-lithography techniques to produce the desired features in the micro-scale, and luminescent tracks when used as nanocomposite inks. The high homogeneity of the films, the uniform distribution of the UCNPs and the easygoing deposition process are the distinctive features of such an approach. Furthermore, the size-dependent thermal properties of UCNPs can be exploited by a proper formulation of the nanocomposites in order to develop materials with high thermal sensitivity and a thermochromic response. Here, we thus present different strategies for designing optical devices through patterning techniques, ink dispensing and multilayer stacking. By applying upconverting nanocomposites with unique thermal responses, local heating effects in designed nanostructures were observed.

Thermoplasmonic enhancement of upconversion in small-size doped NaGd(Y)F4 nanoparticles coupled to gold nanostars.

Plasmon enhancement of luminescence is a common strategy to boost the efficiency of both fluorescence and upconversion via the augmented local electromagnetic field. However, the local heating produced when exciting the plasmon resonance of metallic nanoparticles is often overlooked. As higher temperatures are usually detrimental for radiative processes, only the electromagnetic contribution is exploited for enhancement. We show here that for small size (<20 nm) rare-earth doped ß-NaGd(Y)F4 upconversion nanoparticles (UCNPs), the photothermal properties of gold nanostars (AuNSs) can be used to enhance the total emission intensity. On the contrary, for UCNPs of larger size, the thermoplasmonic effect is adverse for the emissivity. Therefore, we developed a novel strategy to enhance the emission intensity by combining the thermoplasmonic effect on AuNSs with the size-dependent thermal properties of UCNPs. Furthermore, by following the integrated intensity ratio between the emission lines of Er3+, 2H11/2 → 4I15/2 and 4S3/2 → 4I15/2, a direct correlation between the local temperature and the emission intensity could be established. Optical thermometry measurements show that the thermoplasmonic effect in AuNSs, with a plasmon absorption band close to the excitation wavelength, can produce an increment of the local temperature of more than 100 °C when exposed to 976 nm continuous-wave laser light at 50 W cm-2 of power density. The results provided here are relevant for the design and implementation of plasmon-enhanced luminescent devices, upconversion solar-cells, bioprobes and also for hyperthermia.